EP0493217A1 - Procédé pour la conversion de déchets en verre cristallisé - Google Patents

Procédé pour la conversion de déchets en verre cristallisé Download PDF

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Publication number
EP0493217A1
EP0493217A1 EP91403473A EP91403473A EP0493217A1 EP 0493217 A1 EP0493217 A1 EP 0493217A1 EP 91403473 A EP91403473 A EP 91403473A EP 91403473 A EP91403473 A EP 91403473A EP 0493217 A1 EP0493217 A1 EP 0493217A1
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EP
European Patent Office
Prior art keywords
weight
crystallized glass
wollastnite
anorthite
cao
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP91403473A
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German (de)
English (en)
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EP0493217B1 (fr
Inventor
Shigeru Suzuki
Keiichiro C/O Tsukishima Kikai Co. Ltd. Miyano
Takumi c/o Tsukishima Kikai Co. Ltd. Kaneko
Yoshikazu c/o Tsukishima Kikai Co. Ltd Nagayoshi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tokyo Metropolitan Government
Tsukishima Kikai Co Ltd
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Tokyo Metropolitan Government
Tsukishima Kikai Co Ltd
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Publication of EP0493217A1 publication Critical patent/EP0493217A1/fr
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Publication of EP0493217B1 publication Critical patent/EP0493217B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0063Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing waste materials, e.g. slags
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/002Use of waste materials, e.g. slags
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0036Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents

Definitions

  • the present invention relates to a process for converting ashes from the industrial and municipal wastes, such as sludges and the like, to crystallized glass.
  • Conventional methods for manufacturing a structural aggregate materials comprise the steps of: (1) combusting the waste at high temperatures to perform ashing and melting simultaneously; or combusting the waste to form an ash and then to melt the ash at high temperatures; and (2) cooling the melted ash to form a slag.
  • the cooling methods may be roughly divided into two types: one is a water-granulation method in which the melted slag is rapid-cooled by dropping the slag into water to obtain small glassy globules.
  • Another is an annealing method for manufacturing large crystallized slag by annealing the melted slag held in a metal mold.
  • a method for manufacturing crystallized slag is proposed, for example in Japanese Patent Application Second Publication No. 1-24739, which comprises the steps of: (1) preparing a mixture of incinerated ash and other materials so as to have a ratio of (CaO + MgO)/SiO2 of 0.8 to 1.2; (2) melting the mixture at 1350 °C to 1500 °C; (3) crushing the melted mixture by rapid cooling thermal shock; and (4) maintaining the crushed mixture at 1000 °C to 1200 °C for 30 minutes.
  • the water granulation method described above has a disadvantage that the impact strength of the aggregates is low due to its glassy structure.
  • the product thus produced has low bending and impact strengths and it cannot be used as produced. For this reason, all the crystallized slag materials have been used as aggregate materials for such applications as crushed road bed materials.
  • the conventional method for processing slags described above needs a large amount of additives such as calcium when the incineration ash is from municipal wastes or from the dehydrated polymer flocculant which constitutes the main ingredient of such sludges.
  • the processing steps were also slanted towards producing aggregate materials.
  • a processing method for utilizing incineration ashes from waste material sludges using a reduced amount of the additives, not for the purpose of producing aggregate materials but to produce crystallized glasses of superior mechanical and aesthetic properties.
  • One aspect of the present invention is directed to providing a method for manufacturing crystallized glass comprising the steps of:
  • a method for manufacturing crystallized glass which comprises the steps of:
  • the feed material according to the present invention is derived from waste materials such as sludges or municipal wastes, or incinerated ashes from the wastes or other combustibles. These ashes comprise mainly SiO2, Al2O3, CaO, MgO, Fe2O3, P2O5, Na2O, K2O, and the like, similar to the ashes produced from the sludge cakes precipitated with the aid of polymer flocculants.
  • Table 1 The melt properties of an ash of such a composition, such as its melting temperature or the flow temperature, depend on the composition ratio of the ash. For example, if the ratio of CaO/SiO is in the range of 0.8 to 1.2, the melted material can flow out from the furnace at temperatures 1400 °C or less.
  • vitreous material at 800 °C to 900 °C for at least 15 minutes, for example, to precipitate a colloidal crystal such as FeS, and to subsequently maintain the colloidal crystal at 1000 °C to 1200 °C for at least 15 minutes to precipitate the desired needle-shaped crystals such as anorthite (CaO ⁇ Al2O3 ⁇ 2SiO2) or ⁇ -wollastnite (CaO ⁇ SiO2).
  • a colloidal crystal such as FeS
  • desired needle-shaped crystals such as anorthite (CaO ⁇ Al2O3 ⁇ 2SiO2) or ⁇ -wollastnite (CaO ⁇ SiO2).
  • the crystallization process should begin not from the surface regions but from within the melt and progress uniformly throughout the melt. It is known that a nucleating agent aids the crystallization process.
  • sulfur compounds such as FeS or ZnS are suitable as nucleating agents.
  • the iron or sulfur component in the feed material is usually present in the form of oxides such as Fe2O3, Na2SO4, or the like.
  • the carbon (C) component which is present in the feed material can function as a reducing agent to reduce the abundances of oxides such as Fe2O3, Na2SO4 and the like described above. For this reason, the desired FeS can be produced from Fe3+ or Fe2+ obtained in the reduction reaction described above.
  • the feed material including at least one of waste and incineration ashes, having the above-described composition is melted at 1300 °C to 1500 °C to form a melted material.
  • the melted material is degassed as much as possible at 1200 °C to 1400 °C to form a degassed material.
  • the degassed material is poured into a cast-iron mold while the viscosity of the material is maintained at a temperature between 1200 °C to 1300 °C to enable the degassed material to flow from the opening of the furnace.
  • the cast material in the mold is cooled to form a vitreous material.
  • the vitreous material is heat treated in a heat-treatment furnace, preferably at 800 °C to 900 °C for 15 minutes or longer to form a colloidal crystal, and the material is subsequently heat treated at 1000 °C to 1200 °C for 15 minutes or more, preferably 30 minutes or more, to obtain crystals of anorthite or ⁇ -wollastnite having the colloidal crystals as a nucleating agent.
  • the reason for setting the range of SiO2 between 35 to 55 % by weight is that at concentrations less than 35% by weight, the amount is insufficient to form the structure of the crystallized glass including anorthite or ⁇ -wollastnite. If the amount of SiO2 is more than 55% by weight, the quality of the heat-treated crystallized glass deteriorates because the molten material does not flow out from the furnace readily due to the increased viscosity of the molten charge.
  • the amount of Al2O3 is less than 5% by weight, a large amount of additives must be added. If the amount of Al2O3 is more than 20% by weight, the precipitation of the crystals other than anorthite and ⁇ -wollastnite is increased, leading to the deterioration the mechanical properties of the resulting product.
  • the amount of CaO is outside the range of 5% to 30% by weight, the precipitation of the crystals other than anorthite and ⁇ -wollastnite is increased. Furthermore, if the amount of CaO is more than 30% by weight, the amount of additives needed, such as lime, calcium carbonate, or the like is proportionally increased.
  • the amount of Fe2O3 although serving an important function as a flux or a nucleating agent, exceeds 15% by weight, it has an adverse effects on crystallization. If the amount of Fe2O3 is less than 2% by weight, the fluxing effect is reduced, and for this reason, other additives are added or their quantity has to be increased.
  • the reason for adopting the sulphur concentration of 0.2 to 6 % is that 0.2 % is insufficient to provide the needed amount of nucleating agent, including evaporative losses, while over 6 % is excessive.
  • the reason for making the ratio of CaO/(SiO2 + Al2O3) between 0.15 to 0.7 is to precipitate out the crystals of anorthite and ⁇ -wollastnite and to leave about 40 to 60% of the vitreous material as a matrix.
  • the reason for setting the melting temperatures of the feed materials to be 1300 to 1500 °C is that at temperatures below 1300 °C, it becomes difficult to completely melt the feed material, leading to high viscosity, poor fluidity, and premature precipitation of crystallized materials, thus leading to difficulties in producing vitreous materials. At temperatures above 1500 °C, erosion of furnace linings becomes a problem as well as increased radiative losses, thus leading to an uneconomic process.
  • the reason for performing degassing at temperatures between 1200 and 1400 °C is that at 1200 °C, the viscosity of the melt becomes too high for good fluidity while over 1400 °C is uneconomic because of the excessive heating required.
  • the reason for setting the temperature for colloidal crystals formation at 800 to 900 °C is that these crystals form at temperatures between the transition temperature and the melting temperature, but at temperatures below 800 °C, there is little growth of Fe-containing crystals while at temperatures over 900 °C, other crystals begin to precipitate, and therefore the FeS colloidal crystals are not being used effectively as a nucleating agent.
  • the annealing conditions are set at temperature of 1000 to 1200 °C for 15 minutes or more, because at temperatures below 1000 °C, the growth of anorthite and ⁇ -wollastnite is insufficient while above 1200 °C the growth process becomes unstable because of remelting of parts of precipitated crystals and other undesirable effects.
  • the time at temperature is set at 15 minutes, because the crystallization process is incomplete when the holding time is shorter.
  • the glass crystals thus produced have high strength and are stable against chemicals, because the needle-shaped crystals of anorthite and ⁇ -wollastnite are infiltrated with vitreous materials.
  • the crystallized glass material can be melted and poured into a mold to produce a shape, and after stress relieving heat treatment, it can be ground and polished to produce a translucent article of a high product value.
  • the waste ashes obtained from the sewage treatment plants were converted to feed materials having the compositions shown in Table 2 below.
  • Comparative test examples 13 to 15 were produced from the feed materials blended to outside the compositions of the present invention. They were processed under the same processing conditions of melting, degassing, rapid cooling and annealing treatment as the foregoing twelve embodiment samples. The results from the comparative test samples are also shown in Tables 2, 3 and 4. The results of X-ray diffraction analyses are shown in Figure 1, which demonstrated that for the compositions 1 to 8, anorthite crystals were present, and for the compositions 9 to 12, the presence of ⁇ -wollastnite crystals was confirmed. Thermal expansion tests were performed on the base glass, and as a representative example, the results of measurements from embodiment No. 5 are shown in Table 2. The coefficient of expansion ⁇ was 81 x 10 ⁇ 7 which is lower than that for ordinary glasses.
  • the transition temperature and the softening temperature were also higher than those for ordinary glasses by about 100 °C. These are good indications of a glass material having high thermal stability.
  • Table 4 shows the results of testing of the produced samples for their strength, hardness (Moh's hardness), acid resistance and alkaline resistance.
  • Three point bending tests were performed on specimens of 100 x 100 x 8 mm (length x width x thickness), by placing a specimen on two rods of 10 mm diameter, and applying the load through a rod of the same diameter placed at the top midpoint of the specimen.
  • the acid resistance tests were performed with an aqueous solution containing 1 % sulfuric acid, and the alkaline resistance tests were performed with an aqueous solution containing 1 % sodium hydroxide.
  • a sample measuring 15 x 15 x 10 mm size were immersed in respective solutions for 650 hours at 25 °C.
  • test samples are also shown in Table 4 to demonstrate the superiority of the test samples.
  • the results confirmed that the test samples (1-12) were superior to the comparative samples (13-15) or to natural rock (16) in their mechanical strength, impact and chemical stability.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Glass Compositions (AREA)
  • Processing Of Solid Wastes (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
EP91403473A 1990-12-25 1991-12-19 Procédé pour la conversion de déchets en verre cristallisé Expired - Lifetime EP0493217B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2413772A JP2775525B2 (ja) 1990-12-25 1990-12-25 結晶化ガラスの製造方法
JP413772/90 1990-12-25

Publications (2)

Publication Number Publication Date
EP0493217A1 true EP0493217A1 (fr) 1992-07-01
EP0493217B1 EP0493217B1 (fr) 1996-04-17

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US (1) US5203901A (fr)
EP (1) EP0493217B1 (fr)
JP (1) JP2775525B2 (fr)
AT (1) ATE136872T1 (fr)
DE (1) DE69118856T2 (fr)
ES (1) ES2087984T3 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2697451A1 (fr) * 1992-11-04 1994-05-06 Mediterranee Construction Indl Procédé de vitrification de résidus solides issus d'incinération de déchets ménagers et/ou industriels, et produit issu de ce procédé.
EP0652032A1 (fr) * 1993-11-10 1995-05-10 Emc Services Procédé d'inertage de déchets par cristallisation
DE4342934A1 (de) * 1993-12-16 1995-06-22 Otto Feuerfest Gmbh Verfahren zum Recycling von Feuerfestmaterial
ES2078142A1 (es) * 1993-04-16 1995-12-01 Univ La Laguna Reciclaje de cenizas residuales industriales por via vitroceramica.
US5616160A (en) * 1993-05-24 1997-04-01 Corning Incorporated Process for vitrifying incinerator ash
WO1997045376A1 (fr) * 1996-05-29 1997-12-04 De Giovannini S.A. Procede de production d'un materiau amorphe a partir de dechets
GB2324299A (en) * 1997-04-16 1998-10-21 Peter Hay Producing glass ceramic from ferrosilicate powder
ES2270721A1 (es) * 2005-09-12 2007-04-01 Salvador Martinez Manent Metodo para la fabricacion de articulos de vidrio.
CN105967526A (zh) * 2016-05-06 2016-09-28 东莞市银特丰光学玻璃科技有限公司 一种微晶玻璃板的配方及制备工艺

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US5434333A (en) * 1992-09-18 1995-07-18 The United States Of America As Represented By The United States Department Of Energy Method for treating materials for solidification
US5273566A (en) * 1993-01-26 1993-12-28 International Environmelting Corporation Process for producing an environmentally acceptable abrasive product from hazardous wastes
US5369062A (en) * 1993-08-20 1994-11-29 The Research Foundation Of State University Of Ny Process for producing ceramic glass composition
US5508236A (en) * 1993-08-20 1996-04-16 The Research Foundation Of State University Of New York Ceramic glass composition
JPH0867527A (ja) * 1994-08-19 1996-03-12 Hikari Giken:Kk 天然鉱物、一般及び産業廃棄物の焼却灰などを有効に利 用したガラス
US5558690A (en) * 1994-12-23 1996-09-24 Vortec Corporation Manufacture of ceramic tiles from spent aluminum potlining
JPH08310834A (ja) * 1995-05-12 1996-11-26 Hikari Giken:Kk 一般廃棄物の焼却灰等を有効に利用した着色結晶化ガラスの 製造方法
CZ324298A3 (cs) * 1996-04-09 1999-04-14 Vortec Corporation Způsob výroby keramických výrobků z létavého popílku
US5830251A (en) * 1996-04-10 1998-11-03 Vortec Corporation Manufacture of ceramic tiles from industrial waste
JPH1077602A (ja) * 1996-09-02 1998-03-24 Matsushita Sangyo Kk アスファルト舗装材
JP3717018B2 (ja) * 1996-12-11 2005-11-16 ラサ商事株式会社 コンクリート用人工骨材の製造法および製造装置
UA74802C2 (en) 1999-12-06 2006-02-15 Rgs90 A process for producing glass, glass produced by this method and use thereof
KR100477333B1 (ko) * 2002-03-29 2005-03-25 대한민국(순천대학교 총장) 화력발전소 비산재를 이용한 저융점 유리 조성물, 결정화유리 조성물 및 그의 제조방법
KR100465460B1 (ko) * 2002-04-12 2005-01-13 인하대학교 산학협력단 도시소각재를 활용한 결정화유리 제조방법
US9517965B2 (en) * 2012-11-27 2016-12-13 National Institute Of Clean-And-Low-Carbon Energy Method for preparing a soda-lime-silica glass basic formulation and a method for extracting aluminum from coal ash for co-production of glass
CN103482874B (zh) * 2013-09-22 2015-10-21 天津中材工程研究中心有限公司 利用废玻璃低温烧制微晶玻璃板材的方法
JP2015227285A (ja) * 2015-08-10 2015-12-17 Toto株式会社 陶磁器板の製造方法
CN105481255B (zh) * 2016-01-17 2017-10-20 北京清迈华清控股(集团)有限公司 用高硅铁尾矿制造低膨胀微晶玻璃的方法
CN115672938A (zh) * 2022-10-28 2023-02-03 中国科学院过程工程研究所 一种核壳结构玻璃固化体同步稳定固化多元重金属的方法

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0596774A1 (fr) * 1992-11-04 1994-05-11 Constructions Industrielles De La Mediterranee- Cnim Procédé de vitrification de résidus solides issus d'incinération de déchets ménagers et/ou industriels, et produit issu de ce procédé
FR2697451A1 (fr) * 1992-11-04 1994-05-06 Mediterranee Construction Indl Procédé de vitrification de résidus solides issus d'incinération de déchets ménagers et/ou industriels, et produit issu de ce procédé.
ES2078142A1 (es) * 1993-04-16 1995-12-01 Univ La Laguna Reciclaje de cenizas residuales industriales por via vitroceramica.
US5616160A (en) * 1993-05-24 1997-04-01 Corning Incorporated Process for vitrifying incinerator ash
WO1995013116A1 (fr) * 1993-11-10 1995-05-18 Emc Services Procede d'inertage de dechets par cristallisation
FR2712214A1 (fr) * 1993-11-10 1995-05-19 Emc Services Procédé de cristallisation des déchets.
EP0652032A1 (fr) * 1993-11-10 1995-05-10 Emc Services Procédé d'inertage de déchets par cristallisation
DE4342934A1 (de) * 1993-12-16 1995-06-22 Otto Feuerfest Gmbh Verfahren zum Recycling von Feuerfestmaterial
WO1997045376A1 (fr) * 1996-05-29 1997-12-04 De Giovannini S.A. Procede de production d'un materiau amorphe a partir de dechets
GB2324299A (en) * 1997-04-16 1998-10-21 Peter Hay Producing glass ceramic from ferrosilicate powder
ES2270721A1 (es) * 2005-09-12 2007-04-01 Salvador Martinez Manent Metodo para la fabricacion de articulos de vidrio.
WO2007031588A3 (fr) * 2005-09-12 2007-05-10 Manent Salvador Martinez Procede de fabrication d'articles en verre
ES2270721B1 (es) * 2005-09-12 2008-05-16 Salvador Martinez Manent Metodo para la fabricacion de articulos de vidrio.
CN105967526A (zh) * 2016-05-06 2016-09-28 东莞市银特丰光学玻璃科技有限公司 一种微晶玻璃板的配方及制备工艺

Also Published As

Publication number Publication date
ES2087984T3 (es) 1996-08-01
DE69118856T2 (de) 1996-09-05
DE69118856D1 (de) 1996-05-23
JP2775525B2 (ja) 1998-07-16
JPH04317436A (ja) 1992-11-09
US5203901A (en) 1993-04-20
ATE136872T1 (de) 1996-05-15
EP0493217B1 (fr) 1996-04-17

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